Mechanisms for deNOx and deN2O Processes on FAU Zeolite with a Bimetallic Cu-Fe Dimer in the Presence of a Hydroxyl Group-DFT Theoretical Calculations.

In this paper, a detailed mechanism is discussed for two processes: deNOx and deN2O. An FAU catalyst was used for the reaction with Cu-Fe bimetallic adsorbates represented by a dimer with bridged oxygen. Partial hydration of the metal centres in the dimer was considered. Ab initio calculations based on the density functional theory were used. The electron parameters of the structures obtained were also analysed. Visualisation of the orbitals of selected structures and their interpretations are presented. The presented research allowed a closer look at the mechanisms of processes that are very common in the automotive and chemical industries. Based on theoretical modelling, it was possible to propose the most efficient catalyst that could find potential application in industry-this is the FAU catalyst with a Cu-O-Fe bimetallic dimer with a hydrated copper centre. The essential result of our research is the improvement in the energetics of the reaction mechanism by the presence of an OH group, which will influence the way NO and NH3 molecules react with each other in the deNOx process depending on the industrial conditions of the process. Our theoretical results suggest also how to proceed with the dosage of NO and N2O during the industrial process to increase the desired reaction effect.

Change in the Nature of ZSM-5 Zeolite Depending on the Type of Metal Adsorbent-The Analysis of DOS and Orbitals for Iron Species.

Transition-metal-modified zeolites have recently gained the greatest interest among scientists. Ab initio calculations within the density functional theory were used. The exchange and correlation functional was approximated with the Perdew-Burke-Ernzerhof (PBE) functional. Cluster models of ZSM-5 (Al2Si18O53H26) zeolites were used with Fe particles adsorbed above aluminum. The adsorption of three iron adsorbates inside the pores of the ZSM-5 zeolite-Fe, FeO and FeOH-was carried out with different arrangements of aluminum atoms in the zeolite structure. The DOS diagram and the HOMO, SOMO and LUMO molecular orbitals for these systems were analyzed. It has been shown that depending on the adsorbate and the position of aluminum atoms in the pore structure of the zeolite, the systems can be described as insulators or conductors, which significantly affects their activity. The main aim of the research was to understand the behavior of these types of systems in order to select the most efficient one for a catalytic reaction.

Theoretical Studies on the Mechanism of deNOx Process in Cu-Zn Bimetallic System-Comparison of FAU and MFI Zeolites.

In the present study we propose a more promising catalyst for the deNOx process to eliminate harmful nitrogen oxides from the environment. The study was performed with a computer calculation using density functional theory (DFT) based on an ab initio method. Two zeolite catalysts, FAU and MFI, were selected with additional Cu-O-Zn bimetallic dimer adsorbed inside the pores of both zeolites. Based on the analysis of preliminary studies, the most probable way of co-adsorption of nitric oxide and ammonia was selected, which became the initial configuration for the reaction mechanism. Two types of mechanisms were proposed: with hydroxyl groups on a bridged position of the dimer or a hydroxyl group on one of the metal atoms of the dimer. Based on the results, it was determined that the FAU zeolite with a bimetallic dimer and an OH group on the zinc atom was the most efficient configuration with a relatively low energy barrier. The real advantage of the Cu-Zn system over FAU and MFI in hydrothermal conditions has been demonstrated in comparison to a conventional Cu-Cu catalyst.